Reactive carbonate for elastomeric articles

ABSTRACT

This disclosure describes the preparation and use of reactive carbonates containing a metal carbonate bound to a reactive compound, wherein the reactive compound comprises a mineral binding group and a polymer reactive group connected together by a linking group. Such reactive carbonates are useful as reagents in processes for making mineral-bound elastomeric materials, and in methods for reducing cavitation in elastomer materials.

CLAIM OF PRIORITY

This PCT International Application claims the benefit of priority ofU.S. Provisional Application No. 62/571,035, tiled Oct. 11, 2017, thesubject matter of which is incorporated herein by reference in itsentirety.

FIELD OF THE DESCRIPTION

This application relates to materials technology in general and morespecifically to the preparation and use of reactive carbonates capableof imparting certain characteristics of polymeric materials. Thisapplication discloses processes for making mineral-bound elastomericmaterials in which a metal carbonate is bound to the polymer matrix viaa polymer matrix unit comprising a mineral binding group and a linkinggroup. The reactive carbonates disclosed herein can also contain a metalcarbonate bound to a reactive compound including a mineral bindinggroup, a polymer reactive group and a linking group. Such reactivecarbonates are useful, for example, in methods for reducing cavitationin elastomeric materials.

BACKGROUND

Natural rubber latex has been widely used as a protective material forover a century. In recent years, for example, the use of rubber latexgloves has become widespread due in part to the spread of infectiousdiseases such as HIV and AIDS.

Minerals such as calcium carbonate are widely used in elastomericmaterials as filler materials that can alter the properties ofelastomeric articles, and can also reduce the use of more expensivebinder materials. Calcium carbonate is widely used in naturalelastomeric articles such as gloves, and is finding growing use insynthetic rubber articles such as nitrile gloves. Among the mostimportant fillers, calcium carbonate holds the largest market volume andis mainly used in the plastics sector.

In some instances, calcium carbonate and other minerals can producepoints of weakness or cavitation sites in polymeric materials includingelastomeric polymers, particularly when the minerals are poorlydispersed in the polymer matrix. Cavitation is a phenomenon that can beobserved during deformation (such as stretching) of a semi-crystallinepolymeric material. Numerous inclusions (voids or cavities) are formedinside the amorphous phase during deformation of a polymer. The presenceof unwanted inclusions formed by cavitation in elastomeric articles canlead to gradual or even catastrophic failure during use.

For example, in protective gloves formed from natural or syntheticrubber—in which it is often desirable to include minerals such ascalcium carbonate in the rubber matrix to improve properties such asdexterity—a common mode of failure involves leakage or catastrophicfailure at points of repeated deformation (e.g., fingertips). Thesepoints of weakness are often caused by the occurrence of cavitationsites attributed to the presence of fillers such as calcium carbonate,which tend o resist deformation of the elastomer and can therefore leadto inclusions.

Although surface modifications of minerals have been made to improvecompatibility with elastomeric materials, more improvements are neededto enhance the durability of elastomeric materials subject to repeatedstretching and other deformation processes.

SUMMARY

A need exists to discover methods and materials for improving theproperties of elastomeric articles that include mineral materials. Forexample, a need exists to discover methods and materials that arecapable of reducing cavitation in elastomeric articles—thereby improvingthe properties and durability of elastomeric articles such as protectiverubber gloves.

The following disclosure describes the preparation and use of reactiveminerals capable of securely bonding minerals and other inorganic fillermaterials to the polymer matrix of a natural or synthetic elastomers.This secure bonding of minerals and other inorganic filler materials canimprove the properties of elastomeric materials by reducing thefrequency and severity of points of weakness and cavitation sitesoccurring in elastomeric articles.

Embodiments of the present disclosure, described herein such that one ofordinary skill in this art can make and use them, include the following:

(1) Some embodiments relate to a mineral-bound elastomeric material,comprising: an elastic polymer; a polymer matrix unit comprising atleast one connecting group and a mineral binding group; and inclusionsof a metal carbonate bound to the polymer matrix unit via the mineralbinding group, wherein the elastic polymer is covalently bound to thepolymer matrix unit via the linking group;(2) Some embodiments relate to a process for making elastomericcompositions, the process comprising reacting a monomer mixture, aprepolymer, or both, in the presence of a reactive carbonate andoptionally a coupling agent, to obtain a mineral-bound elastomericcomposition, wherein: the reactive carbonate comprises a metal carbonatebound to a reactive compound comprising a mineral binding group and apolymer reactive group connected together by a linking group; and themineral-bound elastomeric composition comprises a polymer matrix towhich the metal carbonate is bound via the mineral binding group;(3) Some embodiments relate to a method or reducing cavitation in anelastomeric material, the method comprising performing a polymerizationor crosslinking process in the presence of a reactive carbonate toobtain a mineral-bound elastomeric material, wherein: the reactivecarbonate comprises a metal carbonate bound to a reactive compoundcomprising a mineral binding group and a polymer reactive groupconnected together by a linking group; and at least one of the followingfactors is controlled such that the mineral-bound elastomeric materialexperiences less cavitation compared to an elastomeric obtained byperforming the polymerization or crosslinking process in the presence ofthe metal carbonate without the reactive carbonate: (a) a proportion ofthe reactive carbonate present in the polymerization process; (b) aparticle size of the metal carbonate the reactive carbonate; (c) astructure of the mineral binding group; (d) a structure of the polymerreactive group; (e) a structure of the linking group; (f) a number ofmineral binding groups contained in the reactive carbonate; and (g) anumber of polymer reactive groups contained in the reactive carbonate;and(4) Some embodiments relate to a reactive carbonate, comprising a metalcarbonate bound to a reactive compound, wherein the reactive compoundcomprises a mineral binding group and a polymer reactive group connectedtogether by a linking group.

Additional objects, advantages and other features of the presentdisclosure will be set forth in part in the description that follows andin part will become apparent to those having ordinary skill in the artupon examination of the following or may be learned from the practice ofthe present disclosure. The present disclosure encompasses other anddifferent embodiments from those specifically described below, and thedetails herein are capable of modifications in various respects withoutdeparting from the present disclosure. In this regard, the descriptionherein is to be understood as illustrative in nature, and not asrestrictive.

DETAILED DESCRIPTION

Embodiments of this disclosure include processes for producing reactiveminerals and mineral-bound polymeric materials formed therefrom. Themineral-bound polymers of the present disclosure have advantages overconventional mineral-filled polymers, because use of the reactiveminerals described herein as additives can provide a polymer matrix inwhich a mineral such carbonate is tightly bound to the polymer matrixvia a polymer matrix unit comprising a mineral binding group and aconnecting group. The connecting group can comprise a saturatedunsaturated organic group comprising 6 to 24 carbon atoms and optionallyat least one atom selected from the group consisting of O, N, S and ahalogen; and the organic group can connect the elastic polymer to themineral binding group. The matrix unit can be formed by performing apolymerization or crosslinking process on a monomer mixture, aprepolymer, or both, in the, presence of the reactive mineral.

Some embodiments relate to a reactive mineral comprising a mineral corebound to a reactive compound, in which the reactive compound comprises amineral binding group and a polymer reactive group connected together bya linking group.

Embodiments of the present disclosure may include any form or mechanismof bonding between the mineral core and the reactive compound such as,for example, ionic bonding and covalent bonding. Without being bound toany particular theory, it is believed that ionic bonding the principleform or mechanism of bonding between the mineral core and the reactivecompound in embodiments wherein the mineral binding group is in the formof a salt.

Although the word “core” implies the “mineral core” may be bound to, orat least partially surrounded by, a plurality of reactive compounds, thepresent disclosure also includes embodiments in which a mineralsubstance is not bound to, at least partially surrounded by, a pluralityof reactive compounds. In some embodiments, the reactive mineral mayformed a plurality of mineral substances bound to a reactive compound.

In some embodiments the mineral comprises a metal salt or a claymineral. For example, the mineral core may be a metal carbonate, a metalhydroxide, a metal phosphate, a metal sulfate and other metal salts ormixtures thereof. In other embodiments the mineral core ay be selectedfrom an aluminum salt, a barium salt, a calcium salt, a magnesium saltand other metal salts or mixtures thereof. For example, the mineral coremay contain at least one metal salt selected from aluminum carbonate,aluminum phosphate, aluminum sulfate, barium carbonate, bariumphosphate, barium sulfate, calcium carbonate, calcium phosphate, calciumsulfate, magnesium carbonate, magnesium phosphate, magnesium sulfate,sodium carbonate, sodium phosphate, sodium sulfate and other metalsalts. In other embodiments the mineral core may contain a metalcarbonate selected from a ground calcium carbonate, a precipitatedcalcium carbonate, and combinations thereof.

When the mineral core is obtained from a naturally occurring source, itmay be that some mineral impurities will inevitably contaminate themineral core. For example, naturally occurring calcium carbonate occursin association with other minerals. Also, in some circumstances, minoradditions of other minerals may be included, for example, one or more ofkaolin, calcined kaolin, wollastonite, bauxite, talc or mica, could alsobe present. In general, however, the mineral core used in theembodiments of the present disclosure will contain less than 5% byweight, for example less than 2 wt %, for example less then 1% by weightof other mineral impurities.

The “mineral binding group” is a functional group capable of binding toa mineral substance used as the mineral core. In some embodiments themineral binding group may include a functional group selected from thegroup consisting of a carboxylic acid, a carboxylic acid salt, acarboxylic acid derivative, an anhydride, an anhydride derivative, aphosphate, a phosphate salt, a phosphate derivative, and a sulfonate.For example, in some embodiments the reactive mineral may be a reactivecarbonate comprising calcium carbonate as the mineral core and areactive compound containing a carboxylic acid salt as the mineralbinding group.

The “polymer reactive group” is a functional group capable of beingincorporated into a polymer matrix by a polymerization reaction, acrosslinking reaction, an endcapping reaction or other bond-formingreaction. For example, in a mineral-bound elastomeric composition formedin the presence of the reactive mineral, the polymer reactive group isgenerally converted from the functional group described above into aunit derived from the functional group. Unlike conventionalsurface-modified fillers used to alter the properties of conventionpolymeric materials, the presence of at least one polymer reactive groupin the reactive minerals of the present disclosure enables the reactiveminerals to become more tightly bound to a polymer matrix due toparticipation of the polymer reactive groups in polymerization orcrosslinking processes that convert the polymer reactive groups intoorganic groups covalently-bound to the polymer matrix. In someembodiments the polymer reactive group may include a functional groupselected from an alkene group, an alkyne group, a halogen group, ahydroxyl group, an ether group, a lactone group, a thiol group, athioester group, an epoxide group, an amine group, an amide group, animine group, an isocyanate group, a sulfide group, a sulfate group, amaleimide group, an acrylate group or mixtures thereof from. In someembodiments the reactive mineral may include a plurality of polymerreactive groups which may the same or different functional group.

The “connecting group” comprises an organic group and a functional groupcapable of being incorporated into a polymer matrix by a polymerizationreaction, a crosslinking reaction, an endcapping reaction or otherbond-forming reaction capable of connecting the polymer to at least onemineral binding group. For example, the organic group can be saturatedor unsaturated and can contain 2 to 30 carbon atoms and optionally atleast one atom selected from the group consisting of O, N, S and ahalogen such that, in a mineral-bound elastomeric composition formedfrom reactive mineral, the organic group and functional group connect apolymer matrix of the elastomeric composition to the mineral bindinggroup. In other embodiments the saturated or unsaturated organic groupmay contain 6 to 24 carbon atoms, or 8 to 20 carbon atoms, or 9 to 15carbon atoms. The functional group can be selected from an alkene group,an alkyne group, a halogen group, a hydroxyl group, an ether group, anester group, a lactone group, a thiol group, thioester group, an epoxidegroup, amine group, an amide group, an imine group, an isocyanate group,a sulfide group, a sulfate group, a maleimide group, an acrylate groupor mixtures thereof from. In some embodiments the connecting groupcontains an aliphatic or aromatic spacer group including the functionalgroup.

The “linking group” is an organic group capable of connecting at leastone mineral binding group to at least one polymer reactive group. Forexample, the linking group may contain a saturated or unsaturatedorganic group containing 2 to 30 carbon atoms and optionally at leastone atom selected from the group consisting of O, N, S and a halogensuch that, in a mineral-bound elastomeric composition formed fromreactive mineral, the organic group connects to the polymer reactivegroup which connects a polymer matrix of the elastomeric composition tothe mineral binding group. In other embodiments the saturated orunsaturated organic group may contain 6 to 24 carbon atoms, or 8 to 20carbon atoms, or 9 to 15 carbon atoms. In some embodiments the linkinggroup contains an aliphatic or aromatic spacer group including afunctional group selected from an ether group, an ester group, an aminegroup, a halogen group, an amide group, an imine group, a sulfide group,a sulfate group, or mixtures thereof.

In some embodiments the organic group of the connecting group or thelinking group is an organic group comprising at least one unsaturatedbond. For example, in some embodiments the linking group is an organicgroup comprising at least one unsaturated bond at a terminal end of theorganic group.

In some embodiments the reactive mineral may comprise a mineral corebound to a reactive compound or polymer matrix unit of either formula(1a) or (1b), or combinations thereof:

(R²)_(d)-(L²)_(c)—(R¹)_(b)-(L¹)—X-Z   (1 a),

wherein:

Z represents a hydrogen atom, a metal ion, or an ammonium ion;

X represents a moiety selected from the group consisting of CO₂, PO₃,PO₄, SO₃, or SO₄

L¹ independently represents a C₁₋₃₀ alkyl group, branched alkyl group, aC₁₋₃₀ alkenyl group, a branched alkenyl group, wherein the alkenyl orbranched alkenyl group can have more than one unsaturated carbon atom, aC₃₋₃₀ group, a C₅₋₃₀ aromatic group or a C₃₋₃₀ heteroaromatic group,said groups optionally including at least one bridging atom selectedfrom the group consisting of O, N and S;

R¹ independently represents an organic group comprising a polymerizablefunctional croup selected from the group consisting of an alkene group,an alkyne group, a halogen group, a hydroxyl group, an ester group, alactone group, a thiol group; a thioester group, an epoxy group, artamine group, and an isocyanate group;

L² independently represents an optimally-substituted C₁₋₃₀ alkylenegroup, an optionally-substituted C₁₋₃₀ alkenylene group, anoptionally-substituted C₃₋₃₀ alicyclic group, an optionally-substitutedC₆₋₃₀ aromatic group or an optionally-substituted C₃₋₃₀ heteroaromaticgroup, said groups optionally including at least one bridging atomselected from the group consisting of O, N and S;

R² independently represents an organic group comprising a polymerizablefunctional group which is branched or unbranched and selected from thegroup consisting of an alkene group, an alkyne group, a halogen group, ahydroxyl group, an ester group, a lactone group, a thiol group, athioester group, an epoxy group, an amine group, and an isocyanategroup;

b represents an integer of 1 to 4;

c represents an integer of 0 to 4; and

d represents an integer of 0 to 4;

OR

A-(X—Y—CO)_(m)(O-B-CO)_(n)OH   (1b)

wherein

A is a moiety containing a terminating ethylenic bond with one or moreadjacent carbonyl groups;

X is 0 and m is 1 to 4 or X is N and m is 1;

Y is C₁₋₁₈-alkylene or C₂₋₁₈-alkenylene;

B is C₂₋₆-alkylene;

n is 0 to 5;

provided that when A contains two carbonyl groups adjacent to theethylenic group, X is N. B can be substituted by one or more C₁₋₆-alkylgroups which may be linear or branched. The group (O-B-CO)_(n) can bethe residue of one or more different hydroxy carboxylic acids orlactones thereof. B can contain 5 or 6 carbon atoms. Non-limitingexamples of suitable hydroxy carboxylic acids or lactones are 5-hydroxyvaleric acid, 6-hydroxy caproic acid, δ-valerocatone, ε-caprolactone andthe alkyl substituted ε-caprolactones such as 4-methyl, 3-methyl,7-methyl, 5-methyl, 5-tert butyl, 4,4,6-trimethyl and 4,6,6-trimethylε-caprolactone. When the group (O-B-CO)_(n) is the residue of two ormore different hydroxy carboxylic acids or lactones it can be derivedfrom δ-valerolactone and ε-caprolactone. When (O-B-CO)_(n) is derivedfrom two or more different hydroxy carboxylic acids or lactones thereof,6-hydroxy caproic acid or δ-caprolactone can be the major components.

For example, in some embodiments the reactive compound is selected fromβ-carboxyethylacrylate, β-carboxyhexyl maleimide, 10-carboxydecylmaleimide, 5-carboxypentyl maleimide, β-acryloyloxypropanoic acid, ormixtures thereof.

Reactive minerals of this disclosure may be constructed of linkinggroups having unbranched chains and/or branched chains each having oneor more polymer reactive group. The reactive minerals may be constructedof linking groups having a variety of chain lengths, including mixturesof reactive minerals constructed of different linking groups having avariety of chain lengths.

Reactive minerals may be produced by combining a mineral core such ascalcium carbonate with a reactive compound, in which the combining mayoccur in dry form or as a slurry of the calcium carbonate and thereactive compound in water, an organic solvent, or a combinationthereof. Prior to the combining step, the mineral core may be subjectedto wet or drying grinding in order to set the particle characteristicsof the mineral core. Such wet or dry grinding and/or the combining stepmay occur in the presence or absence of a dispersant.

In some embodiments the reactive mineral is a reactive carbonatecomprising a metal carbonate bound to the reactive compound. Forexample, the metal carbonate may be an alkali metal carbonate or analkaline earth metal carbonate. In other embodiments the metal carbonateis selected from magnesium carbonate, calcium carbonate, strontiumcarbonate or barium carbonate. In still other embodiments the metalcarbonate may be a particular metal carbonate, such as a ground calciumcarbonate (GCC), a precipitated calcium carbonate (PCC), or combinationsthereof.

A particulate calcium carbonate used as the metal carbonate in thepresent disclosure may be obtained from a natural source by grinding(GCC) or may be prepared synthetically by precipitation (PCC), or may bea combination of the two, i.e., a mixture of the naturally derivedground material and the synthetic precipitated material. A PCC used asthe reactive carbonate in the present disclosure may also be ground.

A GCC used as the metal carbonate in the present disclosure may beobtained by grinding a mineral source such as chalk, marble orlimestone, which may be followed by a particle size classification step,in order to obtain a product having the desired degree of fineness. Theparticulate solid material may be ground autogenously, i.e., byattrition between the particles of the solid material themselves, oralternatively, in the presence of a particulate grinding mediumcomprising particles of a different material from the calcium carbonateto be ground. Wet grinding of calcium carbonate involves the formationof an aqueous suspension of the calcium carbonate which may then beground, optionally in the presence of a suitable dispersing agent.Reference may be made to, for example, EP-A-614948 (the contents ofwhich are incorporated by reference in their entirety) for moreinformation regarding the wet grinding of calcium carbonate.

A PCC used as the metal carbonate in the present disclosure may beproduced by any of the known methods available in the art. TAPPIMonograph Series No 30, “Paper Coating Pigments”, pages 34-35 describesthe three main commercial processes for preparing FCC which is suitablefor use in the various embodiments of the present disclosure. In allthree processes, limestone is first calcined to produce quicklime, andthe quicklime is then slaked in water to yield calcium hydroxide or milkof lime. In the first process, the milk of lime is directly carbonatedwith carbon dioxide gas. This process has the advantage that noby-product is formed, and it is relatively easy to control theproperties and purity of the calcium carbonate product. In the secondprocess, the milk of lime is contacted with soda ash to produce, bydouble decomposition, a precipitate of calcium carbonate and a solutionof sodium hydroxide. The sodium hydroxide must be substantiallycompletely separated from the calcium carbonate if this process is to becommercially attractive. In the third main commercial process, the milkof lime is first contacted with ammonium chloride to give a calciumchloride solution and ammonia gas. The calcium chloride solution is thencontacted with soda ash to produce, by double decomposition,precipitated calcium carbonate and a solution of sodium chloride.

The process for making PCC results in very pure calcium carbonatecrystals and water. The crystals can be produced in a variety ofdifferent shapes and sizes, depending on the specific reaction processthat is used. The three main forms of PCC crystals are aragonite,rhombohedral and scalenohedral, all of which are suitable for use in thevarious embodiments of the present disclosure, including mixturesthereof.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral having ad₁₀ ranging from about 0.01 μm to about 2 μm. For example, the reactivemineral may have a d₁₀ ranging from about 0.01 μm to about 1.5 μm orfrom about 0.01 μm to about 1 μm or from about 0.01 μm to about 0.5 μmor from about 0.1 μm to about 2 μm or from about 0.1 μm to about 1.5 μmor from about 0.1 μm to about 1 μm or from about 0.1 μm to about 0.5 μm.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral having ad50 ranging from about 0.3 μm to about 5 μm. For example, the reactivemineral may have a d₅₀ ranging from about 0.4 μm to about 5 μm or fromabout 0.5 μm to about 5 μm or from about 1 μm to about 4.5 μm or fromabout 1 μm to about 4 μm or from about 1 μm to about 2 μm or from about1.5 μm to about 4 μm or from about 2 μm to about 3.5 μm or from about2.5 μm to about 3 μm. In other embodiments the reactive mineral may havea d₅₀ ranging from about 1 μm to about 2 μm, for example from about 1 μmto about 1.75 μm, for example from about 1 μm to about 1.5 μm.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral having ad₉₀ ranging from about 1 μm to about 10 μm. For example, the reactivemineral may have a d₉₀ ranging from about 1 μm to about 9 μm or fromabout 1 μm to about 8 μm or from about 1 μm to about 7 μm or from about1 μm to about 6 μm. In other embodiments the particulate mineral mayhave a d₉₀ ranging from about 2 μm to about 10 μm or from about 2 μm toabout 9 μm or from about 2 μm to about 8 μm or from about 2 μm to about7 μm or from about 2 μm to about 6 μm.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral having ad₉₈ ranging from about 3 μm to about 15 μm. For example, the reactivemineral may have a d₉₈ ranging from about 3 μm to about 14 μm or fromabout 3 μm to about 13 μm or from about 3 μm to about 12 μm or fromabout 3 μm to about 11 μm or from about 3 μm to about 10 μm or fromabout 3 μm to about 9 μm. In other embodiments the reactive mineral mayhave a d₉₈ ranging from about 4 μm to about 12 μm or from about 4 μm toabout 11 μm or from about 4 μm to about 10 μm or from about 4 μm toabout 9 μm.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral havingsteepness factor ranging from about 20 to about 70. For example, thereactive mineral may have a steepness factor ranging from about 20 toabout 65 or from about 20 to about 60 or from about 25 to about 55 orfrom about 30 to about 50 or from about 35 to about 45 or from about 30to about 40.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral having ad₅₀ ranging from about 0.5 μm to about 2 μm, a d₉₈ ranging from about 4μm to about 10 μm and a d₁₀ ranging from about 0.1 μm to about 0.6 μm.The reactive mineral may, for example, also have a d₉₀ ranging fromabout 2 μm to about 6 μm. The reactive mineral may, for example, alsohave a steepness factor ranging from about 20 to about 50.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral having ad₅₀ ranging from about 0.5 μm to about 1.5 μm, a d98 ranging from about4 μm to about 5 μm and a d₁₀ ranging from about 0.1 μm to about 0.4 μm.The reactive mineral may, for example, also have a d₉₀ ranging fromabout 2 μm to about 3 μm. The reactive mineral may, for example, alsohave a steepness factor ranging from about 40 to about 50.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particle mineral having a d₅₀ rangingfrom about 1 μm to about 2 μm, a d₉₈ ranging from about 7.5 μm to about9 μm and a d₁₀ ranging from about 0.3 μm to about 0.4 μm. The reactivemineral may, for example, also have a d₉₀ ranging from about 4.5 μm toabout 5.5 μm. The reactive mineral may, for example, also have asteepness factor ranging from about 20 to about 30.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a articulate reactive mineral having ad₅₀ ranging from about 1 μm to about 2 μm, a d₉₈ ranging from about 5 μmto about 7 μm and a d₁₀ ranging from about 0.4 μm to about 0.6 μm. Thereactive mineral may, for example, also have a d₉₀ ranging from about2.5 μm to about 4 μm. The reactive mineral may, for example, also have asteepness factor ranging from about 45 to about 55.

Unless otherwise stated, particle size properties referred to herein forthe particulate materials such as the reactive mineral are as measuredin a well known manner by sedimentation of the particulate filler ormaterial in a fully dispersed condition in an aqueous medium using aSedigraph 5100 machine as supplied by Micromeritics InstrumentsCorporation, Norcross, Ga., USA (telephone: +17706623620; website:www.micromeritics.com), referred to herein as a “Micromeritics Sedigraph5100 unit”. Such a machine provides measurements and a plot of thecumulative percentage by weight of particles having a size, referred toin the art as the ‘equivalent spherical diameter’ (e.s.d), less thangiven e.s.d values. The mean particle size d₅₀ is the value determinedin this way of the particle e.s.d at which there are 50% by weight ofthe particles which have an equivalent spherical diameter less than thatd₅₀ value. The d₉₈, d₉₀ and the d₁₀ are the values determined in thisway of the particle e.s.d. which there are 98%, 90% and 10% respectivelyby weight of the particles which have an equivalent spherical diameterless than that d₉₈, d₉₀ or d₁₀ value. Steepness factor is defined as(d₃₀/₇₀×100). The particle size properties referred to herein relate tothe particle size properties of the particulate mineral without anycoating.

The reactive mineral of the present disclosure, such as a reactivecarbonate, may be in the form of a particulate reactive mineral having asurface area ranging from about 1 m²/g to about 50 m²/g. For example,the reactive mineral may have a surface area ranging from about 2 m²/gto about 45 m²/g, or from about 3 m²/g to about 40 m²/g or from about 4m²/g to about 35 m²/g or from about 5 m²/g to about 30 m²/g. In otherembodiments the reactive mineral may have a surface area ranging fromabout 1 m²/g to about 15 m²/g or from about 1.5 m²/g to about 14.5 m²/gor from about 2 m²/g to about 14 m²/g or from about 3 m²/g to about 13m²/g or from about 4 m²/g to about 12 m²/g or from about 5 m²/g to about11 m²/g or from about 6 m²/g to about 10 m²/g or from about 7 m²/g toabout 9 m²/g.

The surface area of particulate materials used herein, such as thereactive mineral, may be determined according to the BET method by thequantity of nitrogen adsorbed on the surface of said particles so to asto form a monomolecular layer completely covering said surface(measurement according to the BET method, AFNOR standard X11-621 and 622or ISO 9277). In certain embodiments, specific surface is determined inaccordance with ISO 9277, or any method equivalent thereto. The surfacearea properties referred to herein relate to the surface area ofparticulate materials without any coating.

In some embodiments the reactive mineral is a reactive carbonatecomprising a mineral core of calcium carbonate satisfying at least oneof the following conditions: (i) the calcium carbonate is in the form ofparticles having a d₁₀ ranging from about 0.01 μm to about 2 μm; (ii)the calcium carbonate is in the form of particles having a d₅₀ rangingfrom about 0.3 μm to about 5 μm; (iii) the calcium carbonate is in theform of particles having a d₉₀ ranging from about 1 μm to about 10 μm;(iv) the calcium carbonate is in the form of particles having a d₉₈ranging from about 3 μm to about 15 μm; and (v) the calcium carbonate isin the form of particles having a steepness factor ranging from about 20to about 70.

In some embodiments the reactive mineral is a reactive carbonate inwhich the metal carbonate comprises calcium carbonate and the reactivecompound is an unsaturated carboxylic acid or unsaturated carboxylicacid salt. For example, in some embodiments the reactive mineral is areactive carbonate in which the metal carbonate is calcium carbonate andthe reactive compound is 9-decenoic acid.

As mentioned above, the word “core” implies that the mineral core may bebound to, or at least partially surrounded by, a plurality of reactivecompounds. Thus, in some embodiments the reactive mineral is a reactivecarbonate comprising a metal carbonate core at least partially coveredby a layer of the reactive compound, such that the mineral binding groupis bound directly to a surface of the metal carbonate core.

Embodiments of this disclosure also relate to compositions containingelastomeric material, a reactive mineral such as the reactive carbonatedescribed above, and optionality a crosslinking agent.

Embodiments of this disclosure also include a process for making anelastomeric composition including the steps of reacting a monomermixture, a prepolymer, or both, in the presence of the reactive mineraland optionally a coupling agent, to obtain a mineral-bound elastomericcomposition in which the mineral core is bound to a polymer matrix viathe mineral binding group.

For example, some embodiments relate to a process for making anelastomeric composition in which a monomer mixture, a prepolymer, orboth, are reacted in the presence of a reactive carbonate and optionallya coupling agent, to obtain a calcium carbonate-bound elastomericcomposition, wherein the reactive carbonate comprises a metal carbonatebound to a reactive compound comprising a mineral binding group and apolymer reactive group connected together by a linking group, and themineral-bound elastomeric composition comprises a polymer matrix towhich the metal carbonate is bound via the mineral binding group.

The “polymer matrix” may be selected from an elastomeric material suchas an acrylonitrile-butadiene rubber, hydrogenatedacrylonitrile-butadiene rubber, an ethylene propylene diene rubber, afluorocarbon rubber, a chloropropene rubber, a silicone rubber, afluorosilicone rubber, a polyacrylate rubber, an ethylene acrylicrubber, a styrene-butadiene rubber, a polyester urethane rubber, apolyether urethane rubber, a polyester urethane/polyether urethanerubber, a natural rubber, or a mixture thereof.

In some embodiments the process for making an elastomeric compositioninvolves reacting a mixture containing the reactive carbonate and atleast one prepolymer selected from a polyacrylate polymer, anethylene-acrylate polymer, a polyester urethane, a brume isobutyleneisoprene polymer, polybutadiene, a chloroisobutylene isoprene polymer, apolychloroprene, a chlorosulphonated polyethylene, an epichlorohydrinpolymer, an ethylene propylene polymer, an ethylene propylene dienepolymer, a polyether urethane, a fluorocarbon polymer, a fluorosiliconepolymer, a hydrogenated nitrile butadiene polymer, a polyisoprene, anisobutylene isoprene butyl polymer, an acrylonitrile butadiene polymer,a polyurethane, a styrene-butadiene polymer, a styrene ethylene butylenestyrene copolymer, a polysiloxane, a vinyl methyl silicone polymer, anacryonitrile butadiene carboxy polymer, a styrene butadiene carboxypolymer, or mixtures thereof.

As mentioned above the process for making a mineral-bound elastomericcomposition may include the presence of at least one coupling agent.Suitable coupling agents include vulcanization agents, crosslinkingagents, curing agents, accelerators, and mixtures thereof. Such couplingagents can be used to modify an elastomeric material or prepolymer byforming cross-links (bridges) between individual polymer chains, andbetween polymers chains and the polymer reactive group of the reactivecompound. Examples of coupling agents suitable for processes of thepresent disclosure include sulfur-based vulcanization agents,peroxide-based coupling agents, phenol-based coupling agents, metallicand non-metallic oxide-based coupling agents, silane-based couplingagents and urethane-based coupling agents.

Examples, of sulfur-based coupling agents include powdered sulfur,precipitated sulfur, highly dispersible sulfur, surface treated sulfur,insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and thelike. Examples peroxide-based coupling agents include benzoyl peroxide,t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide,2,5-dimethyl-2,5-di(t-butyl peroxy)hexane,2,5-dimethylhexane-2,5-di(peroxyl benzoate), and the like. Examplesphenol resin-based coupling agents include brominated alkylphenol resinsand mixed crosslinking system containing an alkyl phenol resin with ahalogen donor such as tin chloride and chloroprene. Examples ofoxide-based coupling agents include zinc oxide, magnesium oxide,litharge, p-quinone dioxime, p-dibenzoylquinone dioxime,tetrachloro-p-benzoquinone, poly-p-dinitroso benzene,methylenedianiline, and the like.

Examples of accelerators include an aldehyde-ammonia base, a guanidinebase, a thiazole base, a sulfonamide base, a thiuram base, a dithio acidsalt base, a thiourea base, and the like. Specific examples include analdehyde ammonia vulcanization accelerator such as hexamethylenetetramine and the like; a guanidine vulcanization accelerator such asdiphenyl guanidine and the like; a thiazole vulcanization acceleratorsuch as dibenzothiazyl disulfide (DM), 2-mercaptobenzothiazole and itsZn salt, a cyclohexylamine salt, and the like; a sulfonamidevulcanization accelerator such as cyclohexyl benzothiazyl sulfonamide(CBS), N-oxydiethylene benzothiazyl-2-sulfenamide,N-t-butyl-2-benzothiazole sulfonamide, 2-(thymol polynyldithio)benzothiazole, and the like; a thiuram vulcanization acceleratorsuch as tetramethylthiuram disulfide (TMTD), tetraethylthiuramdisulfide, tetramethylthiuram monosulfide (TMTM),dipentamethylenethiuram tetrasulfide, and the like; a dithionatevulcanization accelerator such as Zn-dimethyl dithiocarbamate,Zn-diethyl dithiocarbamate Zn-di-n-butyl dithiocarbamate, Zn-ethylphenyldithiocarbamate, Te-diethyl dithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyl dithiocarbamate, pipecoline pipecolyldithiocarbamate, and the like; and a thiourea vulcanization acceleratorsuch as ethylene thiourea, diethyl thiourea, and the like.

In some embodiments the process for making a mineral-bound elastomericinvolves reacting a vulcanizable elastomer in the presence of thereactive carbonate and a vulcanization agent to obtain a crosslinked,mineral-bound elastomeric composition.

In some embodiments the process for making a mineral-bound elastomericcomposition may be carried in the presence of an additive selected fromwater, an organic solvent, a dispersant, an inorganic filler, an organicfiller, a pigment, an antioxidant, a wax, a radical initiator, an impactmodifier, mixtures thereof. In some embodiments the reacting step of theprocess does not occur in the presence of a silane or silanol.

The process for making a mineral-bound elastomeric composition may becarried out such that the reacting of the monomer mixture, theprepolymer, or both, occurs in the presence of a non-reactive mineral.For example, the reacting may occur in the presence of a non-reactivemineral selected from a non-reactive calcium carbonate, a talc, adiatomaceous earth, a clay, and combinations thereof.

In some embodiments the process for making a mineral-bound elastomericcomposition may be carried out such that a proportion of the metalcarbonate bound in the elastomeric composition ranges from about 0.1 toabout 80, or from about to about 50, or from about 5 to about 30, partsper 100 parts of the polymer matrix.

The present disclosure also includes mineral-bound elastomericcompositions obtained by the process described above, and articlescontaining the mineral-bound elastomeric composition. For example,embodiments of the present disclosure include protective articles suchas rubber garments and gloves formed from the mineral-bound elastomericcompositions. Such articles are expected to exhibit improved propertiessuch as greater material and strength and less cavitation, relative tosimilar articles make from mineral-filled elastomeric compositions.Embodiments also include articles formed from mineral-bound polymercompositions based on other (non-elastomeric) types of polymers such aspolyolefins, polyamides, polycarbonates, polyimides, polyurethanes,polyethylenemines, polyoxymethylenes, polyesters, polyacrylates,polylactic acids, polysiloxanes and copolymers and blends thereof suchas acrylonitrile-butadiene-styrene (ABS) copolymers, and the like.

Embodiments of this disclosure also include a mineral-bound elastomericmaterial containing (1) an elastic polymer, (2) a polymer matrix unitcomprising at least one linking group and a mineral binding group, and(3) inclusions of a mineral core bound to the polymer matrix unit viathe mineral binding group, in which the elastic polymer is covalentlybound to the polymer matrix unit via the linking group.

The “elastic polymer” may be an elastic polymer formed by reacting amonomer mixture, prepolymer, or both, as described above with respect tothe process for making an elastomeric composition. For example, theelastic polymer may be selected from an acrylonitrile-butadiene rubber,hydrogenated acrylonitrile-butadiene rubber, an ethylene propylene dienerubber, a fluorocarbon rubber, a chloropropene rubber, a siliconerubber, a fluorosilicone rubber, a polyacrylate rubber, an ethyleneacrylic rubber, a styrene-butadiene rubber, a polyester urethane rubber,a polyether urethane rubber, a polyester urethane polyether urethanerubber, a natural rubber, or mixtures thereof.

The “polymer matrix unit” is generally formed during the reaction of amonomer mixture, prepolymer, or both, due to the presence of the polymerreactive group described above in the reactive mineral. Given that thelinking group and the mineral binding group of the reactive mineral aregenerally not reacted during the formation of the polymer matrix unit,the polymer matrix unit still contains the linking group and the mineralbinding group. The presence of the mineral binding group in the polymermatrix unit enables the elastic polymer to bind the mineral core in amanner that cannot be attained using traditional non-reactive mineralfillers. This tight binding of mineral core materials (such as calciumcarbonate) in the mineral-bound elastomer materials of the presentdisclosure imparts improved properties such as improved tensilestrength, improved elongation at break, improved Young's Modulus,improved toughness and less cavitation.

In some embodiments the polymer matrix unit may include a pluralitylinking groups.

The “linking group” contained in the polymer matrix unit includes thelinking groups described above in greater detail. For example, thelinking group may include a saturated or unsaturated organic groupcomprising 6 to 24 carbon atoms and optionally at least one atomselected from the group consisting of O, N, S and a halogen. In linkinggroups of the present disclosure the organic group connects the elasticpolymer to the mineral binding group as described above.

In mineral-bound elastomeric materials of the present disclosure, the“mineral binding group” and the “mineral core” may defined as describedabove with respect to the reactive mineral. For example, the mineralbinding group may include a functional group selected from the groupconsisting of a carboxylic acid, a carboxylic acid salt, a carboxylicacid derivative, an anhydride, an anhydride derivative, a phosphate, aphosphate salt, a phosphate derivative, and a sulfonate—and the mineralcore may be a metal carbonate, a metal hydroxide, a metal phosphate, ametal sulfate and other metal salts or mixtures thereof.

In some embodiments the mineral core may be selected from an aluminumsalt, a barium salt, a calcium salt, a magnesium salt and other metalsalts or mixtures thereof. The mineral core may contain at least onemetal salt selected from aluminum carbonate, aluminum phosphate,aluminum sulfate, barium carbonate, barium phosphate, barium sulfate,calcium carbonate, calcium phosphate, calcium sulfate, magnesiumcarbonate, magnesium phosphate, magnesium sulfate, sodium carbonate,sodium phosphate, sodium sulfate and other metal salts, in otherembodiments the mineral core may contain a metal carbonate selected froma ground calcium carbonate, a precipitated calcium carbonate, andcombinations thereof.

For instance, in some embodiments the mineral-bound elastomericmaterials may contain a carboxylic acid or salt thereof as the mineralbinding group, and may contain is an alkali metal carbonate or analkaline earth metal carbonate as the mineral core.

The “inclusions” contained in the mineral-bound elastomer materials arein the form of bodies or particles of the mineral core that aredifferent from the organic portion of the elastic polymer. As explainedabove the inclusions of a mineral core, such as a metal carbonate, arebound to the polymer matrix unit via the mineral binding group. Theinclusions may have any shape or size, as long as the inclusions aremeasurably different from the organic portion of the elastic polymer.

In some embodiments the inclusions satisfy at least one of the followingconditions: (i) the inclusions comprise particles of the metal carbonatehaving a d₁₀ ranging from about 0.01 μm to about 2 μm; (ii) theinclusions comprise particles of the metal carbonate having a d₅₀ranging from about 0.3 μm to about 5 μm; (iii) the inclusions compriseparticles of the metal carbonate having a d90 ranging from about 1 μm toabout 10 μm; (iv) the inclusions comprise particles of the metalcarbonate having a d₉₈ ranging from about 3 μm to about 15 μm; and(v)the inclusions comprise particles of the metal carbonate having asteepness factor ranging from about 20 to about 70.

In some embodiments a proportion of inclusions smaller than 0.1 μm is nomore than about 5% by volume, relative to a total volume of themineral-bound elastomeric material. In other embodiments a proportion ofinclusions smaller than 0.1 μm is no more that about 3% by volume, or 2%by volume, or 1% by volume, relative to the total volume of themineral-bound elastomer material.

Mineral-bound elastomer materials of the present disclosure may alsoinclude additional components such that, for example, water, an organicsolvent, a dispersant, an inorganic filler, an organic filler, apigment, an antioxidant, a wax, an impact modifier, and mixturesthereof.

Particulate tillers that may also be contained in mineral-boundelastomer materials of the present disclosure include, for example, analkaline earth metal carbonate (for example dolomite, i.e. CaMg(CO₃)₂),a metal sulfate (for example gypsum), a metal silicate, a metal oxide(for example titania, iron oxide, chromia, antimony trioxide or silica),a metal hydroxide (e.g. alumina trihydrate), a wollastonite, a bauxite,a talc (for example, French chalk), a mica, a zinc oxide (for example,zinc white or Chinese white), a titanium dioxide (for example, anataseor rutile), a zinc sulphide, a calcium carbonate (for exampleprecipitated calcium carbonate (PCC), ground calcium carbonate (GCC),for example obtained from limestone, marble and/or chalk, orsurface-modified calcium carbonate), a barium sulfate (for example,barite, blanc fixe or process white), an alumina hydrate (for example,alumina trihydrate, light alumina hydrate, lake white or transparentwhite), a clay (for example kaolin, calcined kaolin, China clay orbentonite), a silica- or silicate-based mineral (e.g. diatomaceousearth), a zeolite, or blends thereof.

The present disclosure also includes articles containing themineral-bound elastomeric composition. For example, embodiments of thepresent disclosure include protective articles such as rubber garmentsand gloves formed from the mineral-bound elastomeric compositions. Sucharticles are expected to exhibit improved properties such as increasedtoughness and strength, with less cavitation, relative to similararticles make from mineral-filled elastomeric compositions. For example,some embodiments relate to protective gloves containing a mineral-boundelastomer composition that resists cavitation. Embodiments also includearticles formed from mineral-bound polymer compositions based on other(non-elastomeric) types of polymers such as polyolefins, polyamides,polycarbonates, polyimides, polyurethanes, polyethylenemines,polyoxymethylenes, polyesters, polyacrylates, polylactic acids;polysiloxanes and copolymers and blends thereof such asacrylonitrile-butadiene-styrene (ABS) copolymers, just to name a few.

Some embodiments relate to a method for reducing cavitation in anelastomeric material, which involves performing a polymerization orcrosslinking process in the presence of a reactive mineral to obtain amineral-bound elastomeric material, wherein: (1) the reactive mineralcomprises a mineral core bound to a reactive compound comprising amineral binding group and a polymer reactive group connected together bya linking group; and (2) at least one of the following factors iscontrolled such that the mineral-bound elastomeric material experiencesless cavitation compared to an elastomer obtained by performing thepolymerization or crosslinking process in the presence of the mineralcore without the reactive mineral: (a) a proportion of the reactivemineral present in the polymerization process; (b) a particle size ofthe mineral core in the reactive mineral; (c) a structure of the mineralbinding group; (e) a structure of the polymer reactive group; (e) astructure of the linking group; (f) a number of mineral binding groupscontained in the reactive mineral; and (g) a number of polymer reactivegroups contained in the reactive mineral.

The “mineral core,” “mineral binding group,” “polymer reactive group”,“connecting group”, and “linking group” in the method for reducingcavitation correspond to the same components as described above. Forexample, in some embodiments the reactive mineral is a reactivecarbonate comprising a metal carbonate bound to the reactive compound.

As explained above, cavitation is a phenomenon in which inclusions inthe form of voids or cavities are formed inside the amorphous phase of apolymer. Cavitation often occurs during deformation (such as stretching)of a semi-crystalline polymeric material. The formation of unwantedinclusions by cavitation is especially problematic in elastomericmaterials, and often leads to gradual or even catastrophic failureduring use.

In accordance with the various embodiments of the present disclosure,cavitation can be mitigated (reduced or even eliminated) by preparingelastomer is compositions in the presence of a reactive mineral. Withoutbeing bound to any theory, it is believed that mineral-bound elastomericmaterials of the present disclosure reduce cavitation relative toconventional mineral-filled elastomer materials, because the mineralcore in elastomeric compositions described herein is more tightly boundto the polymer matrix via the mineral binding group—which itself iscovalently bound to the polymer matrix.

Because the rigidity of the mineral core bound to the polymer matrix isdirectly affected by the properties of the connecting group and mineralbinding group, or bound to the reactive component which is directlyaffected by the properties of the mineral binding group, the polymerreactive group and the linking group, it is possible to modulate thecavitation characteristics of the mineral-bound elastomeric material bycontrolling factors such as: the structure of the mineral binding group;the structure of the polymer reactive group; the structure of thelinking group; the structure of the connecting group; the number ofmineral binding groups contained in the reactive mineral and the numberof polymer reactive groups contained in the reactive mineral, andcombinations thereof. Furthermore, the cavitation characteristics of themineral-bound elastomeric material can be further modulated bycontrolling: the proportion of the reactive mineral present in thepolymerization process; the particle size of the mineral core in thereactive mineral, and a combination thereof.

In some embodiments the method for reducing cavitation involvesperforming a crosslinking process in the presence of a reactivecarbonate comprising calcium carbonate bound to a reactive compoundcomprising: a carboxylic acid salt as the mineral binding group; and analkene group or an alkyne group as the polymer reactive group. In otherembodiments the mineral-bound elastomeric material is formed bycrosslinking an elastomer in the presence of the reactive carbonate anda coupling agent, such as a vulcanization agent. Suitable couplingagents and vulcanization agents are described above.

Certain combinations of factors may be controlled in order to moreeffectively reduce cavitation in elastomeric materials. For example, insome embodiments the cavitation experienced by the mineral-boundelastomeric material reduced by controlling: number carbon atoms in thelinking group or connecting group; a number of, or size of, organicbranching groups contained in the linking group or connecting group; anumber of polymer reactive groups contained in the reactive carbonate;and combinations thereof.

Embodiments

Embodiment [1] relates to a process for making an elastomericcomposition, the process comprising reacting a monomer mixture, aprepolymer, or both, in the presence of a reactive carbonate andoptionally a coupling agent, to obtain a mineral-bound elastomericcomposition, wherein: the reactive carbonate comprises a metal carbonatebound to a reactive compound comprising a mineral binding group and apolymer reactive group connected together by a linking group; and themineral-bound elastomeric composition comprises a polymer matrix towhich the metal carbonate bound via mineral binding group.

Embodiment [2] relates to the process of Embodiment [1], wherein themetal carbonate metal carbonate or an alkaline earth metal carbonate.

Embodiment [3] relates to the process of Embodiment [1] and [2], whereinthe metal carbonate is selected from the group consisting of a groundcalcium carbonate, a precipitated calcium carbonate, and combinationsthereof.

Embodiment [4] relates to the process of Embodiments [1]-[3], whereinthe mineral binding group comprises at least one functional groupselected from the group consisting of a carboxylic acid, a carboxylicacid salt, a carboxylic acid derivative, an anhydride, an anhydridederivative, a phosphate, a phosphate salt, a phosphate derivative and asulfonate.

Embodiment [5] relates to the process of Embodiments [1]-[4], whereinthe polymer reactive group comprises at least one polymerizablefunctional group selected from the group consisting of an alkene group,an alkyne group, a halogen group, a hydroxyl group, an ester group, alactone group, a thiol group, a thioester group, an epoxide group, anamine group, an isocyanate group, a maleimide group, an acrylate groupand combinations thereof.

Embodiment [6] relates to the process of Embodiments [1]-[5], wherein:the linking group comprises a saturated or unsaturated organic groupcomposing 6 to 24 carbon atoms and optionally at least one atom selectedfrom the group consisting of O, N, S and a halogen, and the organicgroup connects the polymer matrix to the mineral binding group.

Embodiment [7] to the process of Embodiments [1]-[6]; wherein thereactive compound is a compound of formula (1a) or (1b); (1a):(R²)_(d)-(L²)_(c)—(R¹)_(b)-(L¹)—X-Z, wherein: Z represents a hydrogenatom, a metal ion, or an ammonium ion; X represents a moiety selectedfrom the group consisting at CO₂, PO₃, PO₄, SO₃, or SO₄ L¹ independentlyrepresents a C₁₋₃₀ alkyl group, branched alkyl group, a C₁₋₃₀ alkenylgroup, a branched alkenyl group, a C₃₋₃₀ alicyclic group, a C₆₋₃₀aromatic group or a C₃₋₃₀ heteroaromatic group, said groups optionallyincluding at least one bridging atom selected from the group consistingof O, N and S; R¹ independently represents an organic group comprising apolymerizable functional group selected from the group consisting of analkene group, an alkyne group, a halogen group, a hydroxyl group, anester group; a lactone group, a thiol group, a thioester group, an epoxygroup, an amine group, and an isocyanate group; L² independentlyrepresents an optionally-substituted C₁₋₃₀ alkylene group, anoptionally-substituted C₁₋₃₀ alkenylene group, an optionally-substitutedC₃₋₃₀ alicyclic group, an optionally-substituted C₆₋₃₀ aromatic group oran optionally-substituted C₃₋₃₀ heteroaromatic group, said groupsoptionally including at least one bridging atom selected from the groupconsisting of O, N and S; R² independently represents an organic groupcomprising a polymerizable functional group which is branched orunbranched and selected from the group consisting of an alkene group, analkyne group, a halogen group, a hydroxyl group, an ester group, alactone group, a thiol group, a thioester group, an epoxy group, anamine group, and an isocyanate group; b represents an integer of 1 to 4;c represents an integer of 0 to 4; and d represents an integer of 0 to4; OR (1b) A-(X—Y—CO)_(m)(O-B-CO)_(n)OH, wherein A is a moietycontaining a terminating ethylenic bond with one or more adjacentcarbonyl groups; X is O and m is 1 to 4 or X is N and m is 1; Y isC₁₋₁₈-alkylene or C₂₋₁₈-alkenylene; B is C₂₋₆-alkylene;

n is 0 to 5: provided that when A contains two carbonyl groups adjacentto the ethylenic group, X is N.

Embodiment [8] relates the process of Embodiments [1]-[7], wherein: themetal carbonate comprises calcium carbonate; and the reactive compoundis an unsaturated carboxylic acid or unsaturated carboxylic acid salt.

Embodiment [9] relates to the process of Embodiments [1]-[8], whereinthe metal carbonate is calcium carbonate and the reactive compound is9-decenoic acid.

Embodiment [10] relates to the process of Embodiments [1]-[9], whereinthe reactive carbonate comprises a metal carbonate core at leastpartially covered by a layer of the reactive compound, such that themineral binding group is bound directly to a surface of the metalcarbonate core.

Embodiment [11] relates to the process of Embodiments [1]-[10], whereinthe polymer matrix is selected from the group consisting of anacrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadienerubber, an ethylene propylene diene rubber, a fluorocarbon rubber, achloropropene rubber, a silicone rubber, a fluorosilicone rubber, apolyacrylate rubber, an ethylene acrylic rubber, a styrene-butadienerubber, a polyester urethane rubber, a polyether urethane rubber, apolyester urethane/polyether urethane rubber and a natural rubber.

Embodiment [12] relates to the process of Embodiments [1]-[11],comprising reacting a mixture containing the reactive carbonate and atleast one prepolymer selected from the group consisting of apolyacrylate polymer, an ethylene-acrylate polymer, a polyesterurethane, a bromo isobutylene isoprene polymer, a polybutadiene, achloroisobutylene isoprene polymer, a polychloroprene, achlorosulphonated polyethylene, an epichlorohydrin polymer, an ethylenepropylene polymer; an ethylene propylene diene polymer, a polyetherurethane, a fluorocarbon polymer, a fluorosilicone polymer, ahydrogenated nitrile butadiene polymer, a polyisoprene, an isobutyleneisoprene butyl polymer, an acrylonitrile butadiene polymer, apolyurethane, a styrene-butadiene polymer, a styrene ethylene butylenestyrene copolymer, a polysiloxane, a vinyl methyl silicone polymer, anacryonitrile butadiene carboxy polymer and a styrene butadiene carboxypolymer.

Embodiment [13] relates to the process of Embodiments [1]-[12], whereinthe reacting occurs in the presence of at least one selected from thegroup consisting of water, an organic solvent, a dispersant, aninorganic filler, an organic filler, a pigment, an antioxidant, a wax, aradical in a coupling agent and an impact modifier.

Embodiment [14] relates to the process of Embodiments [1]-[13],comprising reacting a vulcanizable elastomer in the presence of thereactive carbonate and a vulcanization agent to obtain a crosslinked,mineral-bound elastomeric composition.

Embodiment [15] relates to the process of Embodiments [1]-[14], whereinthe reacting does not occur in the presence of a silane or silanol.

Embodiment [16] relates to the process of Embodiments [1]-[15], whereinthe reacting of the monomer mixture, the prepolymer, or both, occurs inthe presence of a non-reactive mineral selected from the groupconsisting of a non-reactive calcium carbonate, a talc, a diatomaceousearth, a clay and combinations thereof.

Embodiment [17] relates to the process of Embodiments [1]-[16], whereina proportion of metal carbonate bound in the elastomeric compositionranges from about 0.1 to about 80, or from about 1 to about 50, or fromabout 5 to about 30, parts per 100 parts of the polymer matrix.

Embodiment [18] relates a mineral-bound elastomeric composition obtainedby the process according to the process of Embodiments [1]-[17].

Embodiment [19] relates to an article comprising a mineral-boundelastomeric composition obtained by the process according to Embodiments[1]-[17].

Embodiment [20] relates to a mineral-bound elastomeric material,comprising: an elastic polymer; a polymer matrix unit comprising atleast one connecting group and a mineral binding group; and inclusionsof a metal carbonate bound to the polymer matrix unit via the mineralbinding group, wherein the elastic polymer is covalently bound to thepolymer matrix unit via the connecting group.

Embodiment [21] relates to the mineral-bound elastomeric material ofEmbodiment [20], wherein the elastic polymer is selected from the groupconsisting of an acrylonitrile-butadiene rubber, hydrogenatedacrylonitrile-butadiene rubber, an ethylene propylene diene rubber, afluorocarbon rubber, a chloropropene rubber, a silicone rubber, afluorosilicone rubber, a polyacrylate rubber, an ethylene acrylicrubber, a styrene-butadiene rubber, a polyester urethane rubber, apolyether urethane rubber, a polyester urethane/polyether urethanerubber, and a natural rubber.

Embodiment [22] relates to the mineral-bound elastomeric material ofEmbodiment [20] and [21], wherein: the connecting group comprises asaturated or unsaturated organic group comprising 6 to 24 carbon atomsand optionally at least one atom selected from the group consisting ofO, N, S and a halogen; and the organic group connects the elasticpolymer to the mineral binding group.

Embodiment [23] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[22], wherein the matrix unit comprises a group offormula (1a) or (1b); (1a): (R²)_(d)-(L²)_(c)—(R¹)_(b)-(L¹)—X-Z,wherein: Z represents a hydrogen atom, a metal ion, or an ammonium ion;X represents a moiety selected from the group consisting at CO₂, PO₃,PO₄, SO₃, or SO₄ L¹ independently represents a C₁₋₃₀ alkyl group,branched alkyl group, a C₁₋₃₀ alkenyl group, a branched alkenyl group, aC₃₋₃₀ alicyclic group, a C₆₋₃₀ aromatic group or a C₃₋₃₀ heteroaromaticgroup, said groups optionally including at least one bridging atomselected from the group consisting of O, N and S; R¹ independentlyrepresents an organic group comprising a polymerizable functional groupselected from the group consisting of an alkene group, an alkyne group,a halogen group, a hydroxyl group, an ester group; a lactone group, athiol group, a thioester group, an epoxy group, an amine group, and anisocyanate group; L² independently represents an optionally-substitutedC₁₋₃₀ alkylene group, an optionally-substituted C₁₋₃₀ alkenylene group,an optionally-substituted C₃₋₃₀ alicyclic group, anoptionally-substituted C₆₋₃₀ aromatic group or an optionally-substitutedC₃₋₃₀ heteroaromatic group, said groups optionally including at leastore bridging atom selected from the group consisting of O, N and S; R²independently represents an organic group comprising a polymerizablefunctional group which is branched or unbranched and selected from thegroup consisting of an alkene group, an alkyne group, a halogen group ahydroxyl group, an ester group, a lactone group, a thiol group, athioester group, an epoxy group, an amine group, and an isocyanategroup; b represents an integer of 1 to 4; c represents an integer of 0to 4; and d represents an integer of 0 to 4; OR (1b)A-(X—Y—CO)_(m)(O-B-CO)_(n)OH, wherein A is a moiety containing aterminating ethylenic bond with one or more adjacent carbonyl groups; Xis O and m is 1 to 4 or X is N and m is 1; Y is C₁₋₁₈-alkylene orC₂₋₁₈-alkenylene; B is C₂₋₆-alkylene;

n is 0 to 5: provided that when A contains two carbonyl groups adjacentto the ethylenic group, X is N.

Embodiment [24] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[23], wherein the mineral binding group comprises acarboxylic acid or salt thereof.

Embodiment [25] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[24], wherein the metal carbonate is an alkali metalcarbonate or an alkaline earth metal carbonate.

Embodiment [26] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[25], wherein the metal carbonate is calcium carbonate,and the mineral binding group is a carboxylic acid salt.

Embodiment [27] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[26], wherein the inclusions of the metal carbonatesatisfy at least one of the following conditions: (i) the inclusionscomprise particles of the metal carbonate having a d₁₀ ranging fromabout 0.01 μm to about 2 μm; (ii) the inclusions comprise particles ofthe metal carbonate having a d₅₀ ranging from about 0.3 μm to about 5μm; (iii) the inclusions comprise particles of the metal carbonatehaving a d₉₀ ranging from about 1 μm to about 10 μm; (iv) the inclusionscomprise particles of the metal carbonate having a d₉₈ ranging fromabout 3 μm to about 15 μm; and (v) the inclusions comprise particles ofthe metal carbonate having a steepness factor ranging from about 20 toabout 70.

Embodiment [28] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[27], wherein a proportion of inclusions smaller than0.1 μm is no more than about 5% by volume, relative to a total volume ofthe mineral-bound elastomeric material.

Embodiment [29] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[28], further comprising at least one selected from thegroup consisting of water, an organic solvent, a dispersant, aninorganic filler, an organic filler, a pigment, an antioxidant, a waxand an impact modifier.

Embodiment [30] relates to the mineral-bound elastomeric material ofEmbodiments [20]-[29], wherein the polymer matrix unit comprises aplurality of linking groups.

Embodiment [31] relates to an article comprising the mineral-boundelastomeric material according to Embodiments [20]-[30].

Embodiment [32] relates to a protective glove comprising themineral-bound elastomeric material according to Embodiments [20]-[30] asan elastic material that resists cavitation.

Embodiment [33] relates to a method for reducing cavitation in anelastomeric material, the method comprising performing a polymerizationor crosslinking process in the presence of a reactive carbonate toobtain a mineral-bound elastomeric material, wherein: the reactivecarbonate comprises a metal carbonate bound to a reactive compoundcomprising a mineral binding group and a polymer reactive groupconnected together by a linking group; and at least one of the followingfactors is controlled such that the mineral-bound elastomeric materialexperiences less cavitation compared to an elastomer obtained byperforming the polymerization or crosslinking process in the presence ofthe metal carbonate without the reactive carbonate; (a) a proportion ofthe reactive carbonate present in the polymerization process; (b) aparticle size of the metal carbonate in the reactive carbonate; (c) astructure of the mineral binding group; (d) a structure of the polymerreactive group; (e) a structure of the linking group; (f) a number ofmineral binding groups contained in the reactive carbonate; and (g) anumber of polymer reactive groups contained in the reactive carbonate.

Embodiment [34] relates to the method of Embodiment [33], comprisingperforming a crosslinking process in the presence of a reactivecarbonate comprising calcium carbonate bound to a reactive compoundcomprising: a carboxylic acid salt as the mineral binding group; and analkene group or an alkyne group as the polymer reactive group.

Embodiment [35] relates to the method of Embodiments [33] and [34],wherein the mineral-bound elastomeric material is formed by crosslinkingare elastomer in the presence of the reactive carbonate and avulcanization agent.

Embodiment [36] relates to the method of Embodiments [33]-[35], whereinthe cavitation experienced by the mineral-bound elastomeric material isreduced by controlling at least one of the following factors: (e1) anumber of carbon atoms in the linking group; (e2) a number of, or sizeof, organic branching groups contained in the linking group; and (g) anumber of polymer reactive groups contained in the reactive carbonate.

Embodiment [37] relates to a reactive carbonate, comprising a metalcarbonate bound to a reactive compound, wherein the reactive compoundcomprises a mineral binding group and a polymer reactive group connectedtogether by a linking group.

Embodiment [38] relates to the reactive carbonate of Embodiment [37],wherein: the metal carbonate is an alkali metal carbonate or an alkalineearth metal carbonate; the mineral binding group is a carboxylic acidsalt; the polymer reactive group is an alkene group or an alkyne group;and the linking group is an organic group comprising 6 to 24 carbonatoms.

Embodiment [39] relates to the reactive carbonate of Embodiments [37]and [38], wherein: the metal carbonate is calcium carbonate; and thereactive compound is 9-decenoic acid

Embodiment [40] relates to the reactive carbonate of Embodiments[37]-[39], wherein the linking group is an organic group comprising atleast one unsaturated bond.

Embodiment [41] relates to the reactive carbonate of Embodiments[37]-[40], wherein the linking group is an organic group comprising atleast one unsaturated bond at a terminal end of the organic group.

[42] relates to a composition, comprising: an elastomeric material; thereactive carbonate of Embodiments [37]-[41]; and optionally acrosslinking agent.

Various modifications to the embodiments disclosed herein will bereadily apparent, and the generic principles defined herein may beapplied to other embodiments and applications without departing from thespirit and scope of the present disclosure. Thus, the present disclosureis not intended to be limited to the embodiments shown, but is to beaccorded the widest scope consistent with the principles and featuresdisclosed herein. In this regard, certain embodiments within thedisclosure may not show every benefit of the present disclosure,considered broadly.

1-16. (canceled)
 17. A process for making an elastomeric composition,the process comprising reacting a polymer with a reactive carbonate anda vulcanizing or crosslinking agent, to obtain a mineral-boundelastomeric composition, wherein: the reactive carbonate comprises ametal carbonate bound to a reactive compound comprising a mineralbinding group and a polymer reactive group connected together by alinking group; and the mineral-bound elastomeric composition comprisesthe polymer to which the metal carbonate is bound via the mineralbinding group.
 18. The process according to claim 17, wherein the metalcarbonate is an alkali metal carbonate or an alkaline earth metalcarbonate.
 19. The process according to claim 17, wherein the metalcarbonate is selected from the group consisting of a ground calciumcarbonate, a precipitated calcium carbonate, and combinations thereof.20. The process according to claim 17, wherein the mineral binding groupcomprises at least one functional group selected from the groupconsisting of a carboxylic add, a carboxylic acid salt, a carboxylicacid derivative, an anhydride, an anhydride derivative, a phosphate, aphosphate salt, a phosphate derivative, a sulfonate, phosphoric acid andderivatives, sulfonic acid and derivatives, and combinations thereof.21. The process according to claim 17, wherein the polymer reactivegroup comprises at least one vulcanizable functional group.
 22. Theprocess according to claim 17, wherein the polymer reactive groupcomprises at least one polymerizable functional group selected from thegroup consisting of an alkene group, an alkyne group, a halogen group, ahydroxyl group, an ester group, a lactone group, a thiol group, athioester group, an epoxide group, an amine group, an isocyanate group,a maleimide group, an acrylate group and combinations thereof.
 23. Theprocess according to claim 17, wherein: the linking group comprises asaturated or unsaturated organic group comprising 6 to 24 carbon atomsand optionally at least one atom selected from the group consisting ofO, N, S and a halogen; and the organic group connects the polymer matrixto the mineral binding group.
 24. The process according to claim 17,wherein the reactive compound is a compound of either formula (2) or(2a):b. (R²)_(d)-(L₂)_(c)—(R¹)_(b)-(L¹)—X-Z   (2), wherein: Z represents ahydrogen atom, a metal ion, or an ammonium ion; X represents a moietyselected from the group consisting of CO₂, PO₃, PO₄, SO₃, or SO₄ L¹independently represents a C₁₋₃₀ alkyl group, branched alkyl group, aC₁₋₃₀ alkenyl group, a branched alkenyl group, a C₃₋₃₀ alicyclic group,a C₆₋₃₀ aromatic group or a C₃₋₃₀ heteroaromatic group; R¹ independentlyrepresents an organic group comprising a polymerizable functional groupselected from the group consisting of an alkene group, an alkyne group,a halogen group, a hydroxyl group, an ester group, a lactone group, athiol group, a thioester group, an epoxy group, an amine group, and anisocyanate group; L² independently represents a C₁₋₃₀ alkylene group, aC₁₋₃₀ alkenylene group, a C₃₋₃₀ alicyclic group, a C₆₋₃₀ aromatic groupor a C₃₋₃₀ heteroaromatic group; R² independently represents an organicgroup comprising a polymerizable functional group which is branched orunbranched and selected from the group consisting of an alkene group, analkyne group, a halogen group, a hydroxyl group, an ester group, alactone group, a thiol group, a thioester group, an epoxy group, anamine group, and an isocyanate group; b represents an integer of 1 to 4:c represents an integer of 0 to 4; and d represents an integer of 0 to4; ORA-(X—Y—CO)_(m)(O-B-CO)_(n)OH   (1b) wherein A is a moiety containing aterminating ethylenic bond with one or more adjacent carbonyl groups; Xis O and m is 1 to 4 or X is N and m is 1; Y is C₁₋₁₈-alkylene orC₂₋₁₈-alkenylene; B is C₂₋₆-alkylene; n is 0 to 5: provided that when Acontains two carbonyl groups adjacent to the ethylenic group, X is N.25. The process according to claim 17, wherein: the metal carbonatecomprises calcium carbonate; and the reactive compound is an unsaturatedcarboxylic acid or unsaturated carboxylic acid salt.
 26. The processaccording to claim 17, wherein the metal carbonate is calcium carbonateand the reactive compound is 9-decenoic acid.
 27. The process accordingto claim 17, wherein the reactive carbonate comprises a metal carbonatecore at least partially covered by a layer of the reactive compound,such that the mineral binding group is bound directly to a surface ofthe metal carbonate core.
 28. The process according to claim 17, whereinthe polymer is selected from the group consisting of anacrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadienerubber, an ethylene propylene diene rubber, a fluorocarbon rubber, achloropropene rubber, a silicone rubber, a fluorosilicone rubber, apolyacrylate rubber, an ethylene acrylic rubber, a styrene-butadienerubber, a polyester urethane rubber, a polyether urethane rubber, and anatural rubber.
 29. The process according to claim 17, wherein thereacting occurs in an aqueous environment.
 30. The process according toclaim 17, wherein the reacting occurs in a nonaqueous environment. 31.The process according to claim 30, wherein the reacting occurs in thepresence of a non-aqueous solvent.
 32. The process according to claim17, wherein the reacting occurs in the presence of at least one selectedfrom the group consisting of water, an organic solvent, a dispersant, aninorganic filler, an organic filler, a pigment, an antioxidant, a wax, aradical initiator, a coupling agent and an impact modifier.
 33. Theprocess according to claim 17, wherein the polymer comprises avulcanizable elastomer.
 34. The process according to claim 17, whereinthe reacting does not occur in the presence of a silane or silanol. 35.The process according to claim 17, wherein the reacting of the polymerwith the reactive carbonate and the vulcanizing or crosslinking agentoccurs in the presence of a non-reactive mineral selected from the groupconsisting of a non-reactive calcium carbonate, a talc, a diatomaceousearth, a clay and combinations thereof
 36. The process according toclaim 17, wherein a proportion of metal carbonate bound in theelastomeric composition ranges from about 0.1 to about 80, or from about1 to about 50, or from about 5 to about 30 parts per hundred rubber(PHR)r. 37-48. (canceled)